STUDIES ON KETOSES .7. 5-(ALPHA-D-GLUCOSYLOXYMETHYL)FURFURAL - PREPARATION FROM ISOMALTULOSE AND EXPLORATION OF ITS ENSUING CHEMISTRY

An effective, practical, large-scale adaptable procedure has been deve loped to selectively dehydrate the fructose portion of isomaltulose [g lucosyl-alpha(1-->6)-fructose] (6): heating in DMSO in the presence of a strongly acidic ion-exchange resin generates alpha-D-glucosyloxymet hylfurfural (''alpha-GMF'', 3), isolable in yields up to 70%. A variet y of ensuing reactions have been exploited concerning the generation o f products with industrial application profiles such as aldol-type add itions to the dicyanovinyl (16), nitrovinyl (20), and benzoylvinyl (21 ) derivatives, or to the polymerizable unsubstituted vinyl compound (2 5) and the GMF-acrylic acid (22). Oxidation to GMF-carboxylic acid (11 ) and reductive amination to GMF-amine 8 can be carried out without af fecting the hydroxyl groups in the glucosyl portion; esterification of 11 with long-chain alcohols and N-acylation of 8 with fatty acid chlo rides provide novel surfactants in which hydrophilic and hydrophobic p arts of the molecule are separated by a heteroaromatic spacer.